CN100349941C - Polyoxymethylene copolymers, their preparation and use - Google Patents
Polyoxymethylene copolymers, their preparation and use Download PDFInfo
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- CN100349941C CN100349941C CNB2003101209603A CN200310120960A CN100349941C CN 100349941 C CN100349941 C CN 100349941C CN B2003101209603 A CNB2003101209603 A CN B2003101209603A CN 200310120960 A CN200310120960 A CN 200310120960A CN 100349941 C CN100349941 C CN 100349941C
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- structural unit
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G2/00—Addition polymers of aldehydes or cyclic oligomers thereof or of ketones; Addition copolymers thereof with less than 50 molar percent of other substances
- C08G2/38—Block or graft polymers prepared by polymerisation of aldehydes or ketones on to macromolecular compounds
Abstract
The copolymer comprises a polyoxymethylene block having a structural repeating unit expressed by formula I and a block comprising a structural unit expressed by formula II, wherein R<SP>1</SP>is a divalent group derived from a hydroxy-terminated aliphatic or alicyclic oligomer or polymer, has an ether group and/or a carbonyloxy group in the chain in some cases, and x is a natural number of at least 10.
Description
The present invention relates to novel polyacetal copolymer, and their preparation and application, the especially moulding compound that is used as injection molding and extrudes, to produce various types of moulded products.
Polyoxymethylene (below be also referred to as " POM ") is a kind of high-performance polymer with excellent mechanical properties.Yet its toughness can not satisfy some application, so in some applications impact modifier is added polyoxymethylene.Polyurethane elastomer for example.
Once attempted in the past mixing common component to influence the shock strength of polyoxymethylene by adjustment.Yet these attempt so far not success.
Method of discovery can be mixed selected common component in polyoxymethylene now, and impact modified segmented copolymer is provided.
The invention provides multipolymer, the block that it comprises the polyoxymethylene block of general formula I repeated structural unit and comprises general formula I I structural unit
[-O-CH
2-]
x(I)，[-O-R
1-] (II)，
R wherein
1Be the divalent group that is derived from hydroxy-end capped aliphatic series or cyclic aliphatic oligopolymer or polymkeric substance, wherein ether group and/or phosphinylidyne oxygen groups arranged suitably the time in chain, and x is at least 10 integer.
Multipolymer of the present invention comprises the block be made up of POM-H Acetal homopolymer or multipolymer and the block of general formula I I.
In multipolymer of the present invention, the block ratio of being made up of POM-H Acetal homopolymer or multipolymer is generally 70 to 99wt%, preferred 80-95wt%, and the repeated structural unit ratio of general formula I I is generally 1-30wt%, preferred 5-20wt%, it is benchmark with the multipolymer.
Polyoxymethylene block (" POM block ") is the linearity block of non-branching normally, and it contains 80wt% at least usually, the preferred formaldehyde unit (CH of 90wt% at least
2-O-).
The molecular weight of the POM block in multipolymer of the present invention can change in wide region.X is typically in the scope of 500-10000, preferred 1500-5000.
The term polyoxymethylene block here not only comprises the block derived from formaldehyde homopolymer or its cyclic oligomer such as trioxane ， Si oxane, and comprises the block derived from copolymer component.
Block derived from copolymer component is derived from formaldehyde or its cyclic oligomer, especially trioxane, and cyclic ethers, ring acetal, and/or the polymeric constituent of linear polyacetal.These block arrangement are between the end and/or embedding general formula I I block of segmented copolymer.
The preparation of these POM-H Acetal homopolymer or copolymer block itself is well known by persons skilled in the art, and is described in the document.
Through polymerization, homopolymer block is usually derived from formaldehyde Huo trioxane, preferably in the presence of the catalyzer that is fit to.
In segmented copolymer of the present invention, the preferred copolymer block, especially those remove-CH
2Beyond-O-the repeating unit, also contain and reach 50mol%, preferred 0.1-20mol%, and the common component of 0.5-10mol% especially, be benchmark with the copolymer block, as those derived from oxyethane, 1,2 epoxy prapane, 1, the 2-butylene oxide ring, 1, the 3-butylene oxide ring, 1,3-diox, 1,3-dioxolane and 1,3-two oxa-heptane.
Special preferred block copolymer, wherein the polyoxymethylene block has the repeated structural unit of 99.5-95mol% general formula I, preferably derived from trioxane, and the repeated structural unit derived from above-mentioned comonomer of 0.5-5mol%.
Preferred copolymer, wherein the polyoxymethylene block not only comprises the repeated structural unit of general formula I, also comprises the repeated structural unit of general formula III
(-C
yH
2y-O-)
z (III)，
Wherein, y is the integer of 2-4, and z is the integer of 1-3.
Other POM block that is fit to repeated structural unit that to be the You trioxane prepare with above-mentioned a kind of cyclic ethers and the 3rd monomer reaction, wherein the 3rd monomer preferred formula is R
2-CH
2-Z-CH
2-R
2Difunctional compound, R wherein
2And R
2 'Independent separately is general formula I Va, the group of Ivb or Ivc
Wherein, Z is a chemical bond ,-O-or-O-R
3-O-(R
3=C
2-C
8Alkylidene group or C
2-C
8Cycloalkylidene).
This class preferred monomers is ethylene Racemic glycidol (ethylene diglycidyl), diglycidylether, and, have the diether that 2-8 fat of carbon atom family glycol formed, for example diglycidylether that forms by following substances by 2mol glycidyl compound and 1mol in addition by the diether that glycidyl and polyoxymethylene diox Huo trioxane are formed with 2: 1 mol ratio, this material is: ethylene glycol, 1,4-butyleneglycol, 1, the 3-butyleneglycol, ring fourth-1,3-glycol, 1,2-propylene glycol or hexamethylene-1,4-glycol, or two formal diglycidylethers (diglycerol diformal), what mentioned only is some examples.
Except other the common component that contains general formula I repeated structural unit and POM block when appropriate, segmented copolymer of the present invention comprises the repeated structural unit that covalent linkage is connected to the above-mentioned general formula I I of POM block.
General formula I I repeated structural unit derived from aliphatics or the cycloaliphatic oligopolymer or the polymkeric substance of terminal hydroxy group, contains ether group and/or carbon acyloxy usually in chain when it is suitable.
These can be the straight or branched acyclic oligo or the polymeric hydrocarbyl group of divalence, and hydrocarbyl group preferably contains ethylenic unsaturated bond, for example derived from the group of terminal hydroxy group polyhutadiene.Yet they also can be aliphatic series and/or cyclic aliphatic polyether oligomers or polyether polymer, or aliphatic series and/or cycloaliphatic polyester oligopolymer or polyester polymers, and wherein these are with hydroxy-end capped.
In the present specification scope, term " oligopolymer " meaning is to contain 5-10 repeated structural unit, for example polymkeric substance of ethylene glycol unit continuously.In the present specification scope, the polymkeric substance that has greater than 10 continuous repeated structural units is called " polymkeric substance ".
Be not subjected to any special theory, suppose that these oligopolymer or polymkeric substance embed in the POM block by chain transfer reaction.
These oligopolymer or polymkeric substance can be unsubstituted, or also can be replaced by other aliphatic series and/or cycloaliphatic groups.
Substituent example is the alkyl with 1-6 carbon atom, or has the cycloalkyl of 5-6 ring carbon atom.
Forming the oligopolymer on general formula I I block basis or the example of polymkeric substance is polyalkylene ether, as polyoxyethylene glycol, and polypropylene glycol, poly-(ethylene glycol propylene glycol), or polytetrahydrofuran; And terminal hydroxy group polyhutadiene.
Multipolymer preferably contains general formula I, II repeated structural unit, and contains general formula III repeated structural unit, wherein R in due course
1Be-(C
mH
2m-O)
r-C
mH
2m-group, m are the integers of 2-4, and r is 20-1500, the integer of preferred 50-1000.
M is 2 in the special preferred copolymer.
It is possible that the preparation of multipolymer of the present invention is based on the embedding of finding the repeated structural unit block, as long as between polymerization period, the polyoxymethylene homopolymerization or the multipolymer that generate can be retained in the solution, or remain the fully finely divided state that makes that these blocks can embed of a kind of energy at least.
Under common polymerizing condition, under at 70 ℃ and normal pressure, the POM polymkeric substance of generation precipitates from reaction soln, and therefore serious the obstruction embeds other component by polymerization simultaneously.
Disclosed in the past under High Temperature High Pressure, the mass polymerization of yuban, for example at EP-A-080656, or among the DE-A-4431575.Yet these documents do not provide the indication of segmented copolymer preparation.
Therefore, the present invention also provides a kind of above-mentioned method that contains the multipolymer of general formula I and II repeated structural unit for preparing, and comprises the steps:
I) the initial charge stream that forms by following substances: form-O-CH
2The monomer of-unitary monomer and general formula V, and be generally used for formation-O-CH
2The catalyzer of-unitary monomer polymerization, and the solvent suitably time the, and/or conditioning agent
HO-R
1-OH (V)，
R wherein
1As top defined and
Ii) under 120-300 ℃ temperature and 2 * 10
5-5 * 10
7Carry out copolyreaction under the pressure of handkerchief (2-500 crust).
Formation-O-CH
2-unitary monomeric example, and the monomeric example part in front of general formula V is enumerated out.
In mass polymerization, polyblend preferably is fluid form; As the replacement of above-mentioned form, operation also can be carried out in inert solvent.The example of solvent has aliphatics, cycloaliphatic, or halogenated aliphatic hydrocarbon, or glycol ethers.
The molecular weight of segmented copolymer can be in due course by the conditioning agent commonly used that is used for the POM preparation and/or by select general formula V altogether the molecular weight of component regulate.
The example of operable conditioning agent have acetal and, particularly, the formal of monohydroxy-alcohol, alcohol itself, or as the less water of chain-transfer agent.The conditioning agent consumption reaches 10000ppm usually, preferred 10-3000ppm.
Operable catalyzer or initiator are the cationic initiators that is generally used for the polymethanal polymer preparation.Its example has protonic acid, as fluoridize or the chlorination alkyl-and aryl sulfonic acid trifluoromethanesulfonic acid for example, trifluoromethyl sulfonic acid anhydride, or heteropolyacid, as tungstophosphoric acid, or Lewis acid, as tin tetrachloride, arsenic pentafluoride, phosphorus pentafluoride and boron trifluoride and their title complex compound and salt compounds are as boron trifluoride etherate and triphenyl methylene radical hexafluorophosphate.
The usual amounts of catalyzer or initiator is 0.01-1000ppm, preferred 0.03-10ppm.
According to the present invention, the selection of polymeric area pressure and temperature is that monomer and polymkeric substance are existed with homogeneous phase or finely divided distribution, and preferred dissolving fully mutually or at least fully finely divided to produce a dispersion liquid can also evenly embed component altogether in this dispersion liquid.This is like this for above-mentioned reaction pressure and temperature of reaction numerical value situation.
Copolyreaction is preferably 130-200 ℃ temperature and 5 * 10
5-5 * 10
6Carry out under the pressure of handkerchief (5-50 crust).
The time of polyreaction can change in wide region, typically in 0.1-20 minute scope.Polymerization reaction time is preferably 0.4-5 minute.
Copolyreaction can be carried out in the reactor of known preparation polymethanal polymer.With the tubular reactor of band static mixer, reactor is temperature controllable and withstand voltage design typically.
After polyreaction, polyblend is further handled in common known mode.After the polymerization usually followed by the mixing of inactivation, devolatilization and mixture.
Inactivation is undertaken by add deactivator in reaction mixture.Its example has ammonia, amine, alcohol, or alkali formula reacting salt.
In a special embodiment of the inventive method, final segmented copolymer is water and/or water-soluble alcohol behind preparation technology, as methyl alcohol, at 30-100 ℃, preferably handles down at 50-80 ℃.The result is that the monomer resistates of block component and physical bond is extracted in the reaction mixture, and the mechanical property of its moulded product is improved.
These steps are that those skilled in the art are known, and by for example EP-A-080656 is disclosed.
The fusing point of preferred polyoxymethylene segmented copolymer is at least 150 ℃, molecular weight (number average) Mn in the scope of 50000-300000, preferred 70000-200000.
The polymethanal polymer of preferred especially end group stabilizationization, its link ends contains alkoxyl group, formyloxy, hydroxy alkylidene, or the combination of above-mentioned 2 kinds or multiple group.
Used polyoxymethylene segmented copolymer has 1-50cm usually
3/ 10min melt-flow index (MVR190-2.16, ISO1133).
Polyoxymethylene segmented copolymer of the present invention can be used for all kinds of moulded products, in the technology of processing by injection molding and forcing machine.
Therefore the present invention also provides segmented copolymer to be used for the purposes of above-mentioned purpose.
Because segmented copolymer itself contains the toughness composition of general formula I I, therefore need not to use impact modifying agent usually, as polyurethane elastomer.Yet the adding of said components may be desirable under specific circumstances, and this depends on application requiring.
Segmented copolymer of the present invention can comprise other additive known in the art, and it can add in the preparation segmented copolymer, perhaps can add at once thereafter.
The example of additive is a processing aid, as oxidation inhibitor, and sour trapping agent, formaldehyde-trapping agent, UV stablizer, thermo-stabilizer, adhesion promotor, lubricant, nucleator, or releasing agent, filler, strongthener, or static inhibitor, or give the additive of moulded product specified property, as dyestuff and/or pigment, and/or the additive of electroconductibility is provided, or the mixture of these additives, but do not require scope is defined in the scope of described example.
Segmented copolymer of the present invention can be by mixing fine particle, for example powdery or granulous component and and then carry out thermoplasticity processing and processed, or by heating each component of mixing in the electric hybrid module being suitable for above-mentioned purpose.Electric hybrid module that is fit to and the hybrid technique that is fit to, for example by Saechtling, Kunststoff-Taschenbuch, Hanser Verlag, 27
ThEdtion 1998, and pp.202-217 is disclosed, introduce for referencial use here.
Favourable processing temperature usually in 180-230 ℃ scope, preferred 190-210 ℃.
Following Example is illustrative, and non-limiting the present invention.Unless other explanation is arranged, wherein quantized numerical value is in parts by weight.
The overall operation explanation
Liquid attitude trioxane adds trifluoromethanesulfonic acid as initiator 80 ℃ of polyoxyethylene glycol copolymerization with the two oxa-heptane that are added with formal and (number average) molecular weight 35000 in tubular reactor.Copolymerization is at 155 ℃ and 2.5 * 10
6Carry out under the pressure of handkerchief (25 crust).
1.5 after minute, stop copolymerization by adding triethylamine, and at 185 ℃ through carrying out the decomposition of unstable chain end group in 15 minutes.Substantially volatilize by thermal cutting simultaneous residual monomer, generated porous particle at reactor outlet.
Table 1 has shown monomer, its consumption, and the performance of final copolymer.
With the methanol wash product to remove the adherent residual monomer.The product that so extracts extruded be processed into moulded product.
In selective extraction steps, after grinding to form the particle that diameter is 500 μ m, with product at 60 ℃ with methyl alcohol extracting 20 minutes.By the centrifugal mode methyl alcohol is separated, polymkeric substance removes volatile matter and extrudes in forcing machine.
The composition of the prepared multipolymer of table 1
| Embodiment No. | Trioxane (weight %) | Two oxa-heptane (weight %) | PEG in reaction mixture (weight %) | Initiator concentration (ppm) | MVR (cm 3/10min) |
| 1.1 | 91.6 | 3.4 | 5 | 5 | 4.88 |
| 1.2 | 91.6 | 3.4 | 5 | 6 | 5.03 |
| 1.3 1) | 91.6 | 3.4 | 5 | 6 | 11.93 |
| 2 | 86.6 | 3.4 | 10 | 8 | 32 |
1) the hot extracting by methyl alcohol prepares.
By
1The PEG content of the final segmented copolymer of H NMR spectrometry.Sample dissolution is in hexafluoroisopropanol (HFiP-D
2) in, and under 310K, measure.
The mechanical property of the moulded product that segmented copolymer of the present invention is made is measured as follows:
Tensile stress at break is according to ISO 527-2
Yielding stress is according to ISO 527-2
Notched Izod impact strength is according to EN ISO 179-1
The fracture tension strain is according to ISO 527-2
Yield strain is according to ISO 527-2
Young's modulus is according to ISO 527-2
Density is according to EN ISO 1183-1
Volume melt index MVR 190/2.16,8cm
3/ 10min lists test-results according to EN ISO 1133 following tables 2
The performance of table 2 polyacetal copolymer and Comparative Examples
| Embodiment number | PEG content 3) | Tensile stress at break (MPa) | Yielding stress (MPa) | Notched Izod impact strength (KJ/m 2) | Fracture tension strain (%) | Yield strain (%) | Young's modulus (MPa) | Density (g/l) |
| 1.1 | 4.28 | 50.95 | 59.1 | 9.55 | 39.67 | 13.67 | 2027 | 1.393 |
| 1.3 | 2.69 | 58.21 | 61.8 | 10.34 | 26.71 | 12.03 | 2434 | n.d. |
| 2 | 10.81 | 46.82 | 53.5 | 6.5 | 37.19 | 10.57 | 1958 | 1.385 |
| V1 1) | - | 52.8 | 64.4 | 7.12 | 35.7 | 10.5 | 2650 | 1.41 |
| V2 2) | - | n.d. | 53 | 12 | 32 | 9 | 2100 | 1.39 |
1) is purchased POM; Hostaform
RC9021
2) be purchased impact-resistance POM; Hostaform
RS9063
3) pass through
1H NMR measures
Claims (9)
1. multipolymer, it contains the polyoxymethylene block of general formula I repeated structural unit and contains the block of general formula I I structural unit
[-O-CH
2-]
x(I)，[-O-R
1-] (II)，
R wherein
1Be-(C
mH
2m-O)
r-C
mH
2m-group, m are the integers of 2-4, and r is the integer of 20-1500, and x is at least 10 integer,
Wherein the polyoxymethylene block also comprises the repeated structural unit of general formula III except that the repeated structural unit that comprises general formula I
-(C
yH
2y-O-)
z (III)，
Wherein, y is the integer of 2-4, and z is the integer of 1-3.
2. the described multipolymer of claim 1, wherein x is the integer of 500-10000.
3. the described multipolymer of claim 1, wherein x is the integer of 1500-5000.
4. the described multipolymer of claim 1, wherein r is the integer of 50-1000.
5. the described multipolymer of claim 1, wherein m is 2.
6. prepare the method for the described multipolymer of claim 1, comprise the steps:
I) form initial charge stream by following substances: form-O-CH
2The monomer of-unitary monomer and general formula V, and be generally used for formation-O-CH
2The catalyzer of-unitary monomer polymerization, and non-essential solvent, and/or conditioning agent,
HO-R
1-OH (V)，
R wherein
1As defined in claim 1 and
Ii) 120-300 ℃ temperature and 2 * 10
5-5 * 10
7Carry out copolymerization under the pressure of handkerchief.
7. the described method of claim 6, wherein after preparation, water and/or water-soluble alcohol are handled final segmented copolymer down at 30-100 ℃.
8. the described method of claim 7, wherein after preparation, water and/or water-soluble alcohol are handled final segmented copolymer down at 50-80 ℃.
9. the application of the described multipolymer of claim 1 in producing moulded product.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE10251332.5 | 2002-11-05 | ||
| DE10251332A DE10251332B4 (en) | 2002-11-05 | 2002-11-05 | Polyoxymethylene copolymers, their preparation and use |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1504489A CN1504489A (en) | 2004-06-16 |
| CN100349941C true CN100349941C (en) | 2007-11-21 |
Family
ID=32103318
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2003101209603A Expired - Fee Related CN100349941C (en) | 2002-11-05 | 2003-11-05 | Polyoxymethylene copolymers, their preparation and use |
Country Status (6)
| Country | Link |
|---|---|
| US (3) | US7001959B2 (en) |
| EP (1) | EP1418190A1 (en) |
| JP (1) | JP2004156037A (en) |
| CN (1) | CN100349941C (en) |
| DE (1) | DE10251332B4 (en) |
| TW (1) | TW200413431A (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE10251332B4 (en) * | 2002-11-05 | 2006-07-27 | Ticona Gmbh | Polyoxymethylene copolymers, their preparation and use |
| DE10335959A1 (en) * | 2003-08-04 | 2005-02-24 | Basf Ag | Alcohols as cocatalysts in POM production |
| DE102005016129A1 (en) * | 2005-04-08 | 2006-10-12 | Ticona Gmbh | Process for the preparation of polyoxymethylene homo-and-copolymers and apparatus suitable therefor |
| CN1733675A (en) * | 2005-08-26 | 2006-02-15 | 山东新时代药业有限公司 | Single fluorine substituted methyl ether preparation method |
| US7812110B2 (en) * | 2005-12-24 | 2010-10-12 | Ticona Gmbh | Process for preparation of oxymethylene polymers, selected polymers, and their use |
| US7943726B2 (en) * | 2005-12-24 | 2011-05-17 | Ticona Gmbh | Process for preparation of oxymethylene polymers in a homogeneous phase, and use |
| US20110070125A1 (en) | 2009-09-18 | 2011-03-24 | Brighton Development, LLC | High efficiency polymeric sterilant container assembly |
| US20120193827A1 (en) * | 2010-12-23 | 2012-08-02 | Ticona Llc | Microporous Film |
| WO2012129070A2 (en) * | 2011-03-24 | 2012-09-27 | Unversity Of Florida Research Foundation, Inc. | Acetal metathesis polymerization |
| US9090769B2 (en) | 2011-04-05 | 2015-07-28 | Ticona Llc | Molded articles having a swirl-like or marble-like appearance and compositions for producing same |
| JP5766036B2 (en) * | 2011-06-10 | 2015-08-19 | 旭化成ケミカルズ株式会社 | Process for producing polyacetal block copolymer |
| EP2742077B1 (en) * | 2011-08-11 | 2016-03-23 | Basf Se | Method for processing particulate raw polyoxymethylene |
| JP2016504451A (en) | 2012-12-21 | 2016-02-12 | バイエル・マテリアルサイエンス・アクチェンゲゼルシャフトＢａｙｅｒ ＭａｔｅｒｉａｌＳｃｉｅｎｃｅ ＡＧ | Method for making formaldehyde / CO2 copolymers |
| ES2626498T3 (en) | 2012-12-21 | 2017-07-25 | Covestro Deutschland Ag | NCO modified polyoxymethylene block copolymers |
| CN104937001B (en) * | 2012-12-21 | 2017-03-08 | 科思创德国股份有限公司 | The polyformaldehyde block copolymer of functionalization |
| EP3008100B1 (en) | 2013-06-13 | 2017-03-15 | Covestro Deutschland AG | Polyether carbonate polyoxymethylene block copolymers |
| CN106414532B (en) | 2014-04-07 | 2019-11-01 | 科思创德国股份有限公司 | The method for manufacturing polyformaldehyde block copolymer |
| EP3643730A1 (en) | 2018-10-26 | 2020-04-29 | Covestro Deutschland AG | Method for the preparation of polyoxymethylene polyoxyalkylene block copolymers |
| EP3653657A1 (en) | 2018-11-16 | 2020-05-20 | Covestro Deutschland AG | Method for the preparation of prepolymers comprising a polyoxymethylene block |
| EP3656797A1 (en) | 2018-11-22 | 2020-05-27 | Covestro Deutschland AG | Method for the preparation of polyoxymethylene polyoxyalkylene block copolymers |
| EP3838938A1 (en) | 2019-12-18 | 2021-06-23 | Covestro Deutschland AG | Method for the preparation of polyoxymethylene polyoxyalkylene copolymers |
| EP4015555A1 (en) | 2020-12-18 | 2022-06-22 | Covestro Deutschland AG | Method for preparing a monol or polyol comprising a polyoxymethylene block |
| CN114534654B (en) * | 2022-02-21 | 2023-02-07 | 江苏道尔顿石化科技有限公司 | Post-treatment device and method for passivation and devolatilization of polyformaldehyde powder |
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-
2002
- 2002-11-05 DE DE10251332A patent/DE10251332B4/en not_active Expired - Fee Related
-
2003
- 2003-11-03 US US10/700,195 patent/US7001959B2/en not_active Expired - Fee Related
- 2003-11-03 TW TW092130699A patent/TW200413431A/en unknown
- 2003-11-04 EP EP20030025164 patent/EP1418190A1/en not_active Withdrawn
- 2003-11-05 JP JP2003375146A patent/JP2004156037A/en active Pending
- 2003-11-05 CN CNB2003101209603A patent/CN100349941C/en not_active Expired - Fee Related
-
2005
- 2005-09-14 US US11/226,518 patent/US20060009616A1/en not_active Abandoned
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2008
- 2008-03-28 US US12/058,197 patent/US20080182966A1/en not_active Abandoned
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3754053A (en) * | 1964-05-15 | 1973-08-21 | Celanese Corp | Polyoxymethylene-oxyalkylene block polymers |
| JPH04306215A (en) * | 1991-04-03 | 1992-10-29 | Asahi Chem Ind Co Ltd | Polyacetal block copolymer excellent in lubrication characteristic and its production |
| US20020016395A1 (en) * | 1999-07-30 | 2002-02-07 | Masahiko Niino | Polyacetal block copolymer |
Also Published As
| Publication number | Publication date |
|---|---|
| US20040097691A1 (en) | 2004-05-20 |
| US7001959B2 (en) | 2006-02-21 |
| JP2004156037A (en) | 2004-06-03 |
| DE10251332A1 (en) | 2004-05-19 |
| US20080182966A1 (en) | 2008-07-31 |
| DE10251332B4 (en) | 2006-07-27 |
| TW200413431A (en) | 2004-08-01 |
| US20060009616A1 (en) | 2006-01-12 |
| CN1504489A (en) | 2004-06-16 |
| EP1418190A1 (en) | 2004-05-12 |
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